Grass lignin acylation: p-coumaroyl transferase activity and cell wall characteristics of C3 and C4 grasses

Grasses are a predominant source of nutritional energy for livestock systems around the world. Grasses with high lignin content have lower energy conversion efficiencies for production of bioenergy either in the form of ethanol or to milk and meat through ruminants. Grass lignins are uniquely acylated with p-coumarates (pCA), resulting from the incorporation of monolignol p-coumarate conjugates into the growing lignin polymer within the cell wall matrix. The required acyl-transferase is a soluble enzyme (p-coumaroyl transferase, pCAT) that utilizes p-coumaroyl-CoenzymeA (pCA-CoA) as the activated donor molecule and sinapyl alcohol as the preferred acceptor molecule. Grasses (C3and C4) were evaluated for cell wall characteristics; pCA, lignin, pCAT activity, and neutral sugar composition. All C3 and C4 grasses had measurable pCAT activity, however the pCAT activities did not follow the same pattern as the pCA incorporation into lignin as expected.

[1]  J. Ralph,et al.  Solution-state 2D NMR of Ball-milled Plant Cell Wall Gels in DMSO-d6 , 2008, BioEnergy Research.

[2]  R. Hatfield,et al.  Characterization of p-coumarate accumulation, p-coumaroyl transferase, and cell wall changes during the development of corn stems , 2008 .

[3]  Ronald D. Hatfield,et al.  Composition of cell walls isolated from cell types of grain sorghum stems , 1999 .

[4]  J. Ralph,et al.  Ferulate Cross-Links Limit the Enzymatic Degradation of Synthetically Lignified Primary Walls of Maize , 1998 .

[5]  J. Ralph,et al.  Structural identification of dehydrotriferulic and dehydrotetraferulic acids isolated from insoluble maize bran fiber. , 2006, Journal of agricultural and food chemistry.

[6]  D. Argyropoulos.  Advances in lignocellulosics characterization , 1999 .

[7]  T. Higuchi,et al.  Distribution and roles of p-hydroxycinnamate: CoA ligase in lignin biosynthesis , 1982 .

[8]  J. Grabber,et al.  Relationship of growth cessation with the formation of diferulate cross-links and p-coumaroylated lignins in tall fescue leaf blades , 2002, Planta.

[9]  T. Lam,et al.  Cinnamic acid bridges between cell wall polymers in wheat and phalaris internodes , 1992 .

[10]  T. Lam,et al.  Lignin in wheat internodes. Part 1: The reactivities of lignin units during alkaline nitrobenzene oxidation , 1990 .

[11]  J. Ralph,et al.  Diferulate cross-links impede the enzymatic degradation of non-lignified maize walls , 1998 .

[12]  Ronald D. Hatfield,et al.  Ferulate cross-linking in cell walls isolated from maize cell suspensions , 1995 .

[13]  Richard F. Helm,et al.  Pathway of p-Coumaric Acid Incorporation into Maize Lignin As Revealed by NMR , 1994 .

[14]  P. Weimer,et al.  Degradation characteristics of isolated and in situ cell wall lucerne pectic polysaccharides by mixed ruminal microbes , 1995 .

[15]  J. Ralph,et al.  Characterization of nonderivatized plant cell walls using high‐resolution solution‐state NMR spectroscopy , 2008, Magnetic resonance in chemistry : MRC.

[16]  John Ralph,et al.  A potential role for sinapyl p-coumarate as a radical transfer mechanism in grass lignin formation , 2008, Planta.

[17]  R. Hatfield,et al.  Characterization of a pectic fraction from smooth bromegrass cell walls using an endopolygalacturonase , 1993 .

[18]  C. Crestini,et al.  Structural Analysis of Wheat Straw Lignin by Quantitative 31P and 2D NMR Spectroscopy. The Occurrence of Ester Bonds and α-O-4 Substructures , 1997 .

[19]  J. Ralph,et al.  Facile Synthesis of 4-Hydroxycinnamyl p-Coumarates , 1998 .

[20]  D. Nevins,et al.  Isolation and identification of O-(5-O-feruloyl-α-l-arabinofuranosyl)-1(→3)-O-β-d-xylopyranosyl-(1→4)-d-xylopyranose as a component of Zea shoot cell-walls☆ , 1985 .

[21]  M. Van Montagu,et al.  Modifications in Lignin and Accumulation of Phenolic Glucosides in Poplar Xylem upon Down-regulation of Caffeoyl-Coenzyme A O-Methyltransferase, an Enzyme Involved in Lignin Biosynthesis* , 2000, The Journal of Biological Chemistry.

[22]  D. Buxton,et al.  Forage Cell Wall Structure and Digestibility , 1993 .

[23]  H. Grisebach,et al.  Enzymic synthesis of lignin precursors. Purification and properties of 4-coumarate:CoA ligase from cambial sap of spruce (Picea abies L.). , 2005, European journal of biochemistry.

[24]  S. Kaeppler,et al.  Lax leaf maize: cell wall composition and nutritional value. , 2000 .

[25]  D. R. Buxton,et al.  Cell‐Wall Composition of Maize Internodes of Varying Maturity , 1998 .

[26]  Ronald D. Hatfield,et al.  Solution state NMR of lignins , 1999 .

[27]  R. Hatfield,et al.  Carbohydrate composition of alfalfa cell walls isolated from stem sections differing in maturity , 1992 .

[28]  W. F. Wedin,et al.  Structural Neutral Sugars in Legume and Grass Stems in Relation to Digestibility 1 , 1987 .

[29]  R. Helm,et al.  Lignin/Hydroxycinnamic Acid/Polysaccharide Complexes: Synthetic Models for Regiochemical Characterization , 1993 .

[30]  A. Chesson,et al.  The newly extended maize internode: A model for the study of secondary cell wall formation and consequences for digestibility , 1993 .

[31]  J. Ralph,et al.  p-coumaroylated syringyl units in maize lignin: Implications for β-ether cleavage by thioacidolysis , 1996 .

[32]  Ronald D. Hatfield,et al.  Lignin-ferulate cross-links in grasses: active incorporation of ferulate polysaccharide esters into ryegrass lignins , 1995 .

[33]  J. Ralph,et al.  Using the acetyl bromide assay to determine lignin concentrations in herbaceous plants: some cautionary notes. , 1999, Journal of agricultural and food chemistry.

[34]  T. Lam,et al.  Changes in phenolic acids from internode walls of wheat and phalaris during maturation , 1992 .

[35]  John Ralph,et al.  NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins. , 2003, Organic & biomolecular chemistry.

[36]  M. Mancha,et al.  Synthesis of acyl-CoAs by isolated spinach chloroplasts in relation to added CoA and ATP , 1981, Planta.

[37]  F. Kreuzaler,et al.  Synthesis of p-coumaroyl coenzyme a with a partially purified p-coumarate:CoA ligase from cell suspension cultures of soybean (Glycine max). , 1973, Biochimica et biophysica acta.

[38]  F. Smith,et al.  COLORIMETRIC METHOD FOR DETER-MINATION OF SUGAR AND RELATED SUBSTANCE , 1956 .

[39]  J. D’Auria.  Acyltransferases in plants: a good time to be BAHD. , 2006, Current opinion in plant biology.

[40]  A. Scalbert,et al.  Formation of Ether Linkage between Phenolic Acids and Gramineae Lignin: A Possible Mechanism Involving Quinone Methides , 1986 .

[41]  J. Ralph,et al.  Severe inhibition of maize wall degradation by synthetic lignins formed with coniferaldehyde , 1998 .

[42]  D. C. Smith,et al.  Ester Groups in Lignin , 1955, Nature.

[43]  T. Ishii,et al.  Isolation and characterization of feruloylated arabinoxylan oligosaccharides from bamboo shoot cell-walls. , 1990, Carbohydrate research.

[44]  M. Zenk,et al.  Chemical Syntheses and Properties of Hydroxycinnamoyl- Coenzyme A Derivatives , 1975, Zeitschrift fur Naturforschung. Section C, Biosciences.

[45]  J. Ralph,et al.  Detection and determination of p-coumaroylated units in lignins. , 1999, Journal of agricultural and food chemistry.

[46]  Ronald D. Hatfield,et al.  Identification and synthesis of new ferulic acid dehydrodimers present in grass cell walls , 1994 .

[47]  R. Hartley,et al.  Phenolic constituents of the cell walls of monocotyledons , 1980 .

[48]  Karl Freudenberg,et al.  Constitution and Biosynthesis of Lignin , 1968 .

[49]  R. Hatfield,et al.  Extraction and isolation of lignin for utilization as a standard to determine lignin concentration using the acetyl bromide spectrophotometric method. , 2001, Journal of agricultural and food chemistry.

[50]  A. J. Cairns,et al.  Fructan metabolism in grasses and cereals , 1991 .

[51]  J. Ralph,et al.  Cross-linking of maize walls by ferulate dimerization and incorporation into lignin. , 2000, Journal of agricultural and food chemistry.

[52]  J. Ralph,et al.  Preliminary evidence for sinapyl acetate as a lignin monomer in kenaf. , 2002, Chemical communications.

[53]  T. Ishii,et al.  Linkage of phenolic acids to cell-wall polysaccharides of bamboo shoot. , 1990, Carbohydrate research.

[54]  Jørgen Holst Christensen,et al.  Lignins: Natural polymers from oxidative coupling of 4-hydroxyphenyl- propanoids , 2004, Phytochemistry Reviews.